Leveling and stripping agents



United States Patent LEVELING AND STRIPPING AGENTS Robert Christian Keller, Basel, Switzerland, assignor to Sandoz Ltd., Basel, Switzerland No Drawing. Filed Jan. 30, 1958, Ser. No. 712,066

Claims priority, application Switzerland Feb. 5, 1957 17 Claims. (Cl. 8-84) The present invention relates to leveling and stripping agents.

In accordance with this invention, the said agents are water-soluble compounds, the cation of which-upon complete dissociation of the compounds in aqueous solution-corresponds to the formula aqueous sol ution corresponds to the formula V w l:R-fLOHrGHrOHafI- CEGHNm1] (emornonn enzornonn wherein R, m', n and 12 have the significances set forth in the preceding paragraph, the sum of m+n+p being from to 200, one of the substituents v and w being a lower 2,967,755 Patented Jan. 10, 1961 which can be obtained from high molecular weight fatty acid nitriles by catalytic hydrogenation.

As ethoxylating agents, use may be made for example of ethylene oxide, and also of polyglycols, or monoalkoxy derivatives of the latter, which contain reactive halogen atoms, or of acid polyglycol sulfates. The reaction of the amines with the ethoxylating agents may be carried out according to methods which are per se known. Thus, for example, 10 to 200 mols of ethylene oxide may be added on per mol of amine corresponding to the above given formula, at 140-160 C. in the presence of alkaline catalysts.

The ethoxylated amines can, if desired, be further treated with reagents which are capable of quaternizing basic nitrogen atoms. Such alkylating agents, which may be reacted with the amines in per se known manner, include for example dimethyl sulfate, methyl chloride, benzyl chloride, etc. The products obtained according to the invention are of oily to waxy consistency.

The compounds of the present invention possess valuable interface and surface-active properties, and they have outstanding leveling and stripping capacities for dyestufis. They may be employed together with dyestuffs of diverse types and with compatible mixtures of such dyestuffs, for example, with dyestuffs or dyestuff mixtures which can be employed for dyeing in an alkaline bath, as for example vat dyestuffs, or with neutral drawing dyestuffs such as the direct dyestuffs, or with dyestuffs which draw from an acid bath, such as the metal-free and metalcontaining wool dyestuffs. Theyare also valuable dispersing agents in dyeing with pigments. Thequantity of leveling and stripping agent to be used depends upon alkyl or phenyl(lower)alkyl group and the other one of v and w being H or a lower alkyl or phenyl(lower) alkyl group. The compounds wherein m+n+p is from 25 to 35 and from 150 to 200 are particularly valuable.

- The said compounds are prepared by reacting diamines of the formula RNH.CH CH CH .NH (I) amines, wherein the R groups correspond to the mixture of alkyl groups present in coconut fatty acids, soya fatty acids or tallow fatty acids (commercial stearic acid).

The above-enumerated propylenediamine derivatives can be prepared according to per se conventional processes from primary fatty amines, for example by reacting the fatty amine with acrylonitrile or with B-chloro-pro pionitrile to yield the corresponding cyanoethyl fatty amines, the nitrilo group of which is reduced to the corresponding primary amino group.

By primary fatty amines are meant monoalkylamines the particular conditions, as for example, in accordance with the type and quantity of dyestuffs being employed and upon the character and working condition of the fibrous material being treated. Y In general, it will amount to about 0.1 to about 5%" by weight of the material. The auxiliary agents of the present invention may be added to the dye bath prior to the dyeing operation or in the course of the latter.

The textile material to be treated, for example cotton, regenerated cellulose, wool, silk, casein fibers, polyamide fibers or polyurethane fibers, may be in any desired form, .for example as yarn or fabric or may be loose. The material may be constituted by a single type of fiber or by mixtures of various fibers.

The auxiliary agents according to the invention may be employed in the presenceof bath additions which are usual in dyeing'with the particular dyestuffs or dyestuif being used; thus the auxiliaries may be used in the presence of salts such as sodium sulfate, common salt, ammonium sulfate and sodium acetate, orin the presence of lyes such as caustic soda or inathe presence of acids such as sulfuric acid, phosphoric acid, formic acid and acetic acid, or in the presence of buffer mixtures or of dyestuif carriers or of swelling agents such as o-phenylphenol and dichlorobenzene.

Presently preferred representative embodiments of the invention are set forth in the following illustrative examples. In these examples, the parts and percentages are by weight, and the temperatures are in degrees centigrade.

Example 1 440 parts of ethylene oxide are added on, at to and in the presence of sodium hydroxide as catalyst,

to 400 parts of the commercially available technical propylenediamine of the formula RNH.CH CH,.CH,NH,

wherein R--NH is the tallow amine (Talgamin) radical, the amine being of a purity of about 80% calculated as diamine and melting in the range between about 44 and 48. The resultant product is a brownish product of good water-solubility and of the consistency of oil at ordinary temperature (about 20 to 30). I

Similar brown products of goodwater-solubility are obtained when, in the procedure according to the preceding paragraph, instead of 440 parts of ethylene. oxide, there are used 660, 1100, 1320, 4400, 6600 or'8800 parts of the latter per 400 parts of the diamine. However, the consistency at ordinary temperature of the soobtained products changes with the degree of ethoxylation, increasing from the consistency of oil at the lower degree of ethoxylationthrough the consistency of a salve to the consistency of a soft wax at the. higher degrees of ethoxylation.

Example 2 880 parts of ethylene oxide are added on, at 140l60 and in the presence of 3 parts of sodium hydroxide, to i 320 parts of commercially available technical aminopropylcocosylamine, containing about 80% of amines of the formula set forth in Example 1. A brownish, watersoluble productwhich is oily at ordinary temperature is obtained.

A similar product is obtained if 1320 parts of ethylene oxide are added instead of 880 parts.

Example 3 peratureeoirespdndingitd that of'a'noil or of soff'wax.

i' laaae 4 150 parts .of .technical tridecaethyleneglycol chloride (Polyethyleneglycolchloride 610, Carbide and Carbon Chem. Co.) are admixed with 40 parts of the technical diamine of formula R -NHC C CH NH,

described in Example 1, andthe mixture is maintained at- 130? for 5. hours. The resultant product is. ofsalvelike consistencyatordinary temperature.

h Example 5 40 parts of the technical diamine of formula .R f'NHQ C QH (describcdinrExamples 1 and 4) aredissolvedin 150 parts of technical xylene mixture. 82 parts of technical nonaethyleneglycol .chloride v(Polyethyleneglycolchloi'ide 410, Carbide andICarbon Chem. Co.) are added, and the mixture is refluxed for 3 /2 hours. After cooling the mixture, 8 parts of sodium hydroxide are added in the form of an aqueous solution of 30% strength- The mixture is again boiled for a short time, cooled, and additional 82 parts of Polyethyleneglycolchloride 410 added, and the mixture then maintained at the boil for two more. hours- Afterremovingthe xylene, the water and the sodium chloride, there is obtained a water-soluble product of salve-like consistency.

. Example 6 To mol. of each of the addition products obtained according to Example 1 by '.the addition of 440, 660, 1100, 1320, 4400, 6600 and 8800 parts, respectively, of ethylene oxide onto 400. parts of the amine used in the said example, there are added dropwise in the,,couse of V minutesfand, at. 50.60', 13.9 grams of dimethyl sul fate, after which the mixture is kept at 80 for 30 minutes. The reaction products vary in consistency from oily to soffwaxy, and are all of v'cry'good watcr-solubility.

Example 7 6 parts of potassium hydroxide in the form of an alcoholic potassium hydroxide solution are stirred into 85 parts of the reaction product obtained according to Example 4. Thereupon 7 parts of dimethyl sulfate are .added -at 50-60 and the mixture then maintained at 70-80 for 45 minutes. The brownish, oily reaction product thus obtained is clearly water-soluble.

Example 8 13 parts of benzyl chloride are added dropwise to 172 parts of addition product obtained according to Example 1 from 400 parts of the amine disclosed in the said example and 1320 parts of ethylene oxide, after which the resultant mixture is heated to 120 for one hour. The

obtained reaction product is a brownish, water-soluble course of 45 minutes, and dyeing carried out at the boil 30.

t 60'. was: T te i tsyeia is levell 1 Example 10 l The procedure, accordingto Example Qis'repeated, but heeth xylat qn, productthere emp ycdis replaced h 'aifina .nr q t e ame ed w ime diligent? Exam le .endfihes sktffsf T epla edb ix lenws h au figtss e t Pm 219 Thefdbt'ained dyeing is level.

Example 11 100 parts of wool gabardine are dyed in a bath which consists of 4000 parts of water, 1.2 parts of Solartiirkisblau G LL (C.I., Direct Blue 86), 10 parts of sodium sulfate, 2.5 partsof glacialacetic acid and 1.3 parts of The dyeing isgbegun at :the bath heated to boiling in (the course pf .45 minutes, and the boiling temperature maintainedfo'r 1 hour. There is obtained a leveldyeing,

60., vlylereas in the absence of the product pfthe. present invention the resulting dyeing is skittery.

' Example 12 Nylon'which has been unevenly dyed with 3%,.Xylcnwalkorange R (Schultz, page 280) is moved aboutfor 1 Wool gabardine, dyed with" o f Neolanrot R C.I.,

xeranea 180), is moved about in a bath whichfrelative to theweig'htof the wool,fcontains'3% of sulfuric-acid, 10% of sodium sulfate and 4% of the addition product of 880 parts of ethylene oxide and 4 00 partspf the amine of Example' l. The dyeing is brightened by this treatrnent. I

Example 14 bath isi-prepared from; SODO-parts-oli water, 1 part of Lanasynbraun RL C .I,, Acid Brown 28), 8 parts of s d um s fa e n L pa tn th rea ticn pr du of 400 parts of aminopropylsoyaamine and 6600 'parts of ethylene oxide according to Example 3. 100 parts of loose wool are entered into this bath at 50, after which the temperature of the bath is brought to the boil in the course of 45 minutes, the boiling temperature being maintained for 45 minutes. The resultant dyeing is a level brown.

Example 15 A dyebath is prepared which contains, relative to the weight of the material (wool gabardine) to be dyed, 2% of Omegachromcyan-in GR (Schultz, page 221), 1% of glacial acetic acid, of sodium sulfate and 0.5% of the addition product of 1320 parts of ethylene oxide onto 400 parts of aminopropylsoyaamine according to Example 3. The wool gabardine is entered into the bath in a goods to liquor ratio of 1:40, the temperature of the bath is raised to the boil in the course of 30 minutes, and boiling is continued for 45 minutes. The bath is then cooled to 70 and the dyeing is developed with 1% of potassium bichromate for 30 minutes at the boil. A full, level dyeing is obtained.

Example 16 Cotton is dyed, in a goods to liquor ratio of 1:30, in a bath which contains, relative to the weight of the material to be dyed, 1% of Solarblau 3GLN (C.I., Direct Blue 115), 10% of sodium sulfate and 0.8% of the reaction product from 880 parts of ethylene oxide and 320 parts of aminopropylcocosamine according to Example 2. The rate of bath exhaustion is retarded by the addition of the latter. A like result is obtained when using the reaction product according to Example 5.

Example 17 Example 18 Cotton fabric which had been dyed with 2% of Sandothrenor-ange R (Schultz, page 242) is moved about for one hour at 30-50 and at a goods to liquor ratio of 1:50 in a blank vat which, per 1000 parts, contains 4 parts of sodium dithionite, 25 parts of aqueous caustic soda solution of 30% strength and 0.9 part of the addition product from 1320 parts of ethylene oxide and 400 parts of the amine employed in Example 1 and which has been treated with dimethyl sulfate according to Example 6. The material is then rinsed and hung in the air. The dye is stripped from the fabric.

In the foregoing examples, Schultz" refers to Schultz, Farbstofitabellen, 7th ed., suppl. vol. II (1939), and Cl. refers to Color Index, 2d ed., vol. I (1956), in Examples 13 and 14, and to the corresponding vol. II in Examples 11 and 16.

Having thus disclosed the invention what is claimed 1s:

1. As a dyeing assistant, a water-soluble compound, the cation of which corresponds, upon complete dissociation of the compound in aqueous solution, to the formula wherein R is an aliphatic hydrocarbon radical containing 8 to 22 carbon atoms, each of m, n and p represents a whole number from 0 to 200, the sum of m+n+p amounting to 10 to 200, one of the substituents v and w being a member selected from the group consisting of lower alkyl and pheny1(lower)alkyl, and the other one of the substituents v and w being selected from the group consisting of H, lower alkyl and phenyl(lower) alkyl.

2. As a dyeing assistant, a water-soluble compound as defined in claim 1, wherein the sum of m+n+p amounts to 25 to 35.

3. As a dyeing assistant, a water-soluble compound as defined in claim 1, wherein the sum of m+n+p amounts to to 200.

4. As a dyeing assistant, a water-soluble compound according to claim 1, wherein one of v and w is methyl and the other is H.

5. Asa dyeing assistant, a water-soluble compound according to claim 1, wherein each of v and w is methyl.

6. As a dyeing assistant, a water-soluble compound according to claim 1, wherein one of v and w is benzyl and the other is H.

7. As a dyeing assistant, a water-soluble compound according to claim 1, wherein each of v and w is benzyl.

8. A method of carrying out a textile material-dyeing operation in an aqueous bath containing a dyestulf which is applicable to the textile material, which comprises immersing the textile material in the said bath in the presence in the bath of a water-soluble compound, the cation of which corresponds, upon complete dissociation of the compound in aqueous solution to the formula (oHiOmmmH (OHgCHzO)nH wherein R is an aliphatic hydrocarbon radical containing 8 to 22 carbon atoms, each of m, n and p represents a whole number from 0 to 200, the sum of m+n+p amounting to 10 to 200 and each of x and y being scleoted from the group consisting of H, lower alkyl and phenyl(lower) alkyl.

9. A method of carrying out a textile material-dyeing operation in an aqueous bath containing a dyestufl' which is applicable to the textile material, which comprises immersing the textile material in the said bath in the presence in the bath of a water-soluble compound, the cation of which corresponds, upon complete dissociation of the compound in aqueous solution, to the formula (CH2CH20)mH momma;

wherein R is an aliphatic hydrocarbon radical containing 8 to 22 carbon atoms, each of m, n and p represents a whole number from 0 to 200, the sum of m+n+p amounting to 10 to 200, one of the substituents v and w being a member selected from the group consisting of lower alkyl and phenyl(lower)alkyl, and the other one of the substituents v and w being selected from the group consisting of H, lower alkyl and phenyl(lower) alkyl.

10. A method of carrying out a textile material-dyeing operation in an aqueous bath containing a dyestuff which is applicable to the textile material, which comprises immersing the textile material in the said bath in the presence in the bath of a water-soluble compound, the cation of which corresponds, upon complete dissociation of the compound in aqueous solution, to the formula wherein R is an aliphatic hydrocarbon radical containing 8 to 22 carbon atoms, and each of m, n and 17 represents a whole number from 0 to 200, the sum of m+n+p 7 wherein R is an aliphatic hydrocarbon radical containing 8! to 22 carbon atoms, each of m, n and p represents a wholenumber from to 200, and the sum of m+n+p amounting to to 200. 4

12. As 'a dyeing assistant, a quaternary ammonium compound of the formula .I wherein R is the alkyl radical of tallow amine, eachof m, n and p represents a whole number fromO to 200, and the some of m+n+p amounting to 10 to 200.

13. An aqueous bath for dyeing textile material, said bath containing in solution therein about 0.1% to about 5.0% by weight, relatively to the material to be treated, of a water-soluble compound, the cation of which correspond, upon complete dissociation of the compound in aqueous solution, to the formula wherein R is an aliphatic hydrocarbon radical containing 8 to 22 carbon atoms, each of m, n and p represents a whole number from 0 to 2000, the sum of m+n+p amount to 10 to 200, one of the substituents v and w being a member selected from the group consisting of lower alkyl and phenyl(lower) alkyl, and the other one of the substituents v and w being selected from "the group consisting of H, lower alkyl andphenylflower) alkyl.

14. An aqueous bath for dyeing textile material, said bath containing in solution therein about 0.1% to about 0.5% by weight, relatively to' the material to'be treated, of a compound of the formula i wherein R is an aliphatic hydrocarbon radical containing 8 to 22 carbon atoms, each of m, n and p represents a whole number from 0 to 200, and the sum of m+n+p amounting to 10 to 200.

15. An aqueous bath for dyeing textile material, said, bath containing in solution therein about 0.1%: to about wherein R is an aliphatic hydrocarbon radical containing 8to 22 carbon atoms, each of m, n and 12 represents a.

whole number from 0 to 200, and the sum of m+n+p amounting to 10 to 200.

17. An aqueous bath for dyeing textile material, said bath containing in solution therein about 0.1% to about 0.5% by weight, relatively to the material to be treated, of a compound of the formula T011350 whereinR is thealkyl radical of tallow amine, each of m, n and p represents a whole number from 0 to 200, and the sum of m-i-n-l-p amounting to 10 to 200.

References Cited in the file of this patent UN E TATE AT S 2,619,502 Williamset al. Nov. 25, 1952 2,697,118 Lundsted et' a1. Dec. 14, 1954 2,760,978 Huebner Aug 28, 1956 2,763,530 Schuetz et al Sept. 18, 1956 2,767,214 Bersworth Oct. 16, 1956 2,772,310 Morris Nov. 27, 1956 OTHER REFERENCES Textile Chemicals and Auxiliaries, Speel, Reinhold Publ. Corp, 1952, pp. 328 and 329. 

8. A METHOD OF CARRYING OUT A TEXTILE MATERIAL-DYEING OPERATION IN AN AQUEOUS BATH CONTAINING A DYESTUFF WHICH IS APPLICABLE TO THE TEXTILE MATERIAL, WHICH COMPRISES IMMERSING THE TEXTILE MATERIAL IN THE SAID BATH IN THE PRESENCE IN THE BATH OF A WATER-SOLUBLE COMPOUND, THE CATION OF WHICH CORRESPONDS, UPON COMPLETE DISSOCIATION OF THE COMPOUND IN AQUEOUS SOLUTION TO THE FORMULA 